Urea adducts of quaternary ammonium compounds



Patented Apr. 27, 1954 .asmisa ADDUQTS o 'AMMONIUM CO Alfred W.Weitkam'p, Lansing, .rIll., .Jemmei W.

-1 This invention relates to quate gnary 11111119- nium compounds." Morespecifically; it relates to a novel series of chemical compoundscomposed where thesubstituents onthe nitrogen atomq p "f: i fierfef torganic fadicals and X represents .an anion. jT hese' terials' are'knownto be useful in various .iie1ds,..d l! ndi upon the specificsubstituents contained" therein. They have beeniusedy-for. exam legasgermicides, fungicides, surface-active ,agents, ,therapeutic agents, andthe like. 'Tl'i'eir utilization"hasbeen handicappedl liowever, otvinto-the fact that dia au highl i sqepi ,imaierialsa- -ar thereforeobtained, sticlgypnp'astyme lid ree -sta w i ie enq tqiseqv re iizhaaquat rmr ammonium compounds of.

tam .class can .pe

muls ofi w' ih eure ube n inondonic;.;-do .no -interiere gyvithithe,characteristic, activity ,.of..-..the I aquaternary.ammonium.saltrfonexample, surface lactivitywor. :fungicidahoi.gennicidal lcharater) sses,'".wlfiich.;aiie"d1fiicult,.to.measura hmile, r

" H ...elass awardin tomcthods.describedin theprior tareeeafil -p eka mes bl nde ;andiciis' e iai .-t fireerfl w n n udery- 32 "The... surface.actiuity...of the "quat rn r BR 111 0- .nium...oom15.ound...i:leduces'.' the .surface .tensionam aqueous solutionsof the adduct, and facilitates .spreading-andlpenetration of. the .urea.in, certain applications. All of..these. advantages .replffifient.,Sl1'iking, improvements .over ithe, quaternary .ammoniumicompoundsnofthe .priorgart.

One,..o,bject,. of .burdnventionis to .convert quasternaryammoniumsomnoundsfinto. a. ,form. more readily and conveniently stored,handled,.measiuredhandrapplied. ,.-Another. o.bject. is. to .converturea intoqa more effectiyelyi utilizable; form. .An- .other obj ectis topreparaachemical.combination .of .urea. and ,aquaternary ammonium.compound having, synergistic properties, as ainutrientland .,an.antibiotic ,wheriLemployed in,.p,1ant sprays. iA Jurther. obiectis to,separate quaternary ammo- .nium. compoundsintonlasses according, to,.strucituralhconfi ration. .-.-Other.,objects..of ,ounimzen-.tionmillebe.apparent-front.thefiqescription.thereioiianitheannendednlaims.

;The..pneparation ,of our ..new .sompositions .of amattenisicarried,out, by.,reacting nreawitha .qua-

ternary ammonium compound ..of .our -.defined The qua ernary vammoniumcompound preferably dissolved in n, organic liquid, which serves as adiluent to produce a solution of low iyiscgsi yman h resultin s luti n scont c i s re l d' ureatsplxentata temperatur hetwee gah g lan fi ir -ei ferab b twe n ,,.,a!gout}2 au ifi unt lh re ct on i mmb re .Jnareatiszup q c s a l oithe ired urea dduct in -the, diluent liquid. The 1w;v i ub. .edat ifiltr tiq s tli nd-demother liquor, erefrom. The..wasl1ed @Qsdllil Th idrn olid -the.new...comon ...-Q: Y! iT i9. sutable wi hout iure 11 eatme efonthamany.uses tmwhich itis damnedsuitauled iluents i for the quaternary ,ammo- ,mum.lqompoundsainclude methanol,..ethanol,.. n- ..propyl alcohol, ,isoprppyl, alcohol, n-.butyl alcohol,.k .yle ..s1x, .o an he like --These solvents .afumti nas multan ouslyto. .diss lr th quater- 50 nary-ammonium compounds. and--reduce. the.viscosity thereof, ar d to a tiuate the urea for adduct formation.

. "effor complete-reactioniof .thenuaternary vam- .moriium.compound iith'urea. the ratirfof urea fifi'litdllquateriiary fainmoniumeompoundlshouldbe ep etalpnd ril bet ee abou m a 2 ho rs.

at least one mole of urea per methylene group in the straight-chainorganic radicals containing more than 5 methylene groups which areattached to the nitrogen atom. When substantially pure adducts aredesired, uncontaminated with free urea, a smaller ratio of urea shouldbe employed.

It will be apparent that numerous variations of the above procedure maybe employedfor making our new compositions. The following variations areillustrative:

1. The quaternary ammonium compound in excess is stirred at roomtemperature with a saturated solution of urea in a urea solvent, such asa lower aliphatic (C1 to C6) alcohol. The ad duct that precipitates isfiltered off, washed with a low-boiling solvent such as acetone orether, and dried. The unreacted quaternary ammonium compound in the washliquor is recycled.

2. Theoretical proportions of urea and the quaternary ammonium compoundare dissolved in a lower aliphatic alcohol, and the solution isspraydried.

3. A concentrated solution (for example, 50 to 75 percent by weight) ofthe quaternary ammonium compound in a lower aliphatic alcohol is mixedwith the theoretical proportion of dry powdered urea, the mixture isstirred until it becomes homogeneous, and the resulting slurry is dried.

4. An unsaturated alcoholic solution of urea and a quaternary ammoniumcompound in approximately theoretical proportions is diluted with anorganic liquid which functions as an alcohol solvent and a urea-adductantisolvent. F

Example I Ten grams of a '75 percent by weight solution ofdimethyldilaurylammonium bromide in isopr'opyl alcohol was mixed with asaturated solution of urea in methanol containing ten grams of urea, themixture was agitated approximately minutes at room temperature. Thereaction mixture was then diluted with 50 milliliters of diethyl etherand was filtered. The solids were washed with an additional quantity of(iiethyl ether and were dried in air. The resulting product was a fineWhite powder containing 5.25 percent by weight of bromine. Thiscorresponds to a ratio of one mole of the quaternary ammonium salt to17.6 moles of urea, or 33 percent by weight of quaternary ammonium saltin the urea adduct. Fungicidal tests on the adduct revealed that itsfungicidal potency against Sclerotz'm'a fructz'cola was exactlyproportional to the content of quaternary ammonium salt, the MLD-SQbeing obtained at a concentration of 2.8 milligrams of quaternaryammonium salt per liter, and MLD95 at 5.9 milligrams per liter.

Example II inisopropyl alcohol was treated as described in Example Iwith ten grams of urea in methanol. The resulting white powder analyzed4.15 percent by weight chlorine, corresponding to one mole of ammoniumsalt per 8.6 moles of urea, or 40 percent by weight quaternary ammoniumsalt in the adduct. Consistent with this ratio, the fungicidal MLD-against Sclerotima fructicola was obtained at a concentration of 1.7milligrams of quaternary ammonium salt per liter, and the WILD-95 at 2.4milligrams per liter.

Example III Urea adducts were similarly prepared from the followingquaternary ammonium compounds:

Benzyldimethyllauryloxymethylammonium chloride.Benzyldimethyllaurylthiomethylammonium chloride. Lauryltrimethylammoniumchloride.

The quaternary ammonium compounds from which our novel compositions arederived are substituted dimethylammonium compounds having the followingstructural formula,

where R and R comprise at least one straightchain organic radicalcontaining at least five methylene groups, where R. and R togethercontain not more than one carbocyclic-substituted aliphatic radical,said carbocyclic-substituted aliphatic radical containing not more thansix carbon atoms in the ring, and where X represents an anion, such ashalogen, sulfate, hydroxyl, or nacyloxy group. The said straight-chaingroup may be n-alkyl, n-alkenyl, n-alkynyl, n-alkadienyl, n-oxaalkyln-polythiaalkyl, and the like, where m and n represent zero or positiveintegers which must total at least five, and where X represents halogen.The urea-reactivity of the straight-chain organic radical is notafiected by the substitution thereon of hydroxyl or fluorine in anyposition, or by substitution thereon of other halogen, amino, ormercapto in the omega position. The carbocyclic group may becyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl,and the like, and may contain a halogen, hydroxyi, or mercaptosubstituent in the para position. The most useful group of our newcompositions which we have so far prepared are obtained from quaternaryammonium salts containing one or two Clo-C20 n-alkyl groups. Thesecompounds have excellent germicidal, fungicidal, and surface-activeproperties, which are retained and improved when the compounds arereacted with urea.

Our new compositions are useful in a wide range of applications. Theymay be used as a combination plant food and fungicide for fruit treesand plants in general. For this purpose, they can be conveniently usedas a dust, owing to the fact that they are free-flowing, non-hygroscopicpowders; and they can conveniently be combined with insecticidal agentsand inert materials which are commonly applied separately.

Since garden crops or ornamental plants are commonly dusted in themorning when the plants are wet with dew, the use of our newcompositions or materials comprised thereof at such times is distinctlyadvantageous, permitting rapid decompositionof the urea adduct andimmediate feeding and fungicidal action by the urea and the quaternaryammonium salt. Alternatively, our new compositions can be usedadvantageously as a component of sprays for plants and trees. In thisconnection, the surface-active characteristics of the quaternaryammonium compounds are highly advantageous. When the adduct'is added towater, it decomposes, yielding a solution which has a lower surfacetension than a comparable urea solution and for this reason being morecapable and eificient in feeding nitrogen to plants. If a higher ratioof urea is desired, an additional quantity of urea can be blended withtheadduct, owing to the powdery form of the latter. Our new compositionsare also useful in pharmaceutical preparations, for example in mouthwashes, tooth pastes, and the like. They are especially useful in toothpowders, where their non-hygroscopic nature is essential, and wheretheir combined germicidal and ammonia-producing actions are highlydesirable. Many other uses will be apparent to those skilled in the art.f"

While we have described our invention. in connection with certainspecific embodiments thereof, it is to be understood that we are notlimited thereto. The compositions of our invention are new and usefulbroadly within the scope of the disclosure thereof, and it is further tobe understood that any modifications or equivalents that wouldordinarily occur to one skilled in the art are to be considered as lyingwithin the 'scope of our invention.

In accordance with the foregoing description, we claim as our invention:-j

1. An adduct of urea and a quaternary dimethylammonium compound havingas substituents on the nitrogen atom thereof (1) at least onestraight-chain organic radical containing at least five methylene groupsand (2) an aliphatic radical containing not more than onecarbocyclic-substituent, said carbocyclic substituent containing notmore than six carbon atoms in the ring, said quaternary dimethylammoniumcompound being otherwise free from functional groups reactive with urea.

2. The composition of claim 1 wherein said quaternary dimethylammoniumcompound has as substituents on the nitrogen atom thereof at least oneC:C2o n-alkyl radical.

3. The composition of claim 1 wherein said quaternary dimethylammoniumcompound has as substituents on the nitrogen atom thereof at least onen-oxaalky radical containing at least five methylene groups.

4. The composition of claim 1 wherein said quaternary dimethylammoniumcompound has as substituents on the nitrogen atom thereof at least onen-thiaalkl radical containing at least five methylene groups.

5. An adduct of urea and a quaternary dimethylammonium compound havingas substituents on the nitrogen atom thereof (1) at least onestraight-chain organic radical containing at least five methylene groupsand 2) an aliphatic radical free from cyclic substitutents, saidquaternary dimethylammonium compound being otherwise free fromfunctional groups reactive with urea.

6. An adduct of urea and a dialkyldimethylammonium compound wherein atleast one of said alkyl radicals is an n-alkyl radical containing atleast six carbon atoms.

7. An adduct of urea and a dialkyldimethylammonium salt wherein at leastone of said alkyl radicals is an n-alkyl radical containing at least sixcarbon atoms.

8. An adduct of urea and dimethyldilaurylammonium bromide.

9. An adduct of urea and benzyldimethyllaurylammonium chloride.

10. An adduct of urea and benzyldimethyllauryloxymethylammoniumchloride.

11. An adduct of urea and benzyldimethyllaurylthiamethylammoniumchloride.

12. An adduct of urea and lauryltrimethylammonium chloride.

13. In a method for separating quaternary dimethylammonium compoundsaccording to structural configuration from a mixture thereof, saidmixture comprising a quaternary ammonium compound (I) having assubstituents on the nitrogen atom thereof (1) at least one straightchainorganic radical containing at least five methylene groups and (2) analiphatic radical containing not more than one carbocyclic substituent,said carbocyclic substituent containing not more than six carbon atomsin the ring, said mixture further comprising at least one quaternaryammonium compound (II) of another type, and said mixture beingsubstantially free from components containing functional groups reactivewith urea, the steps which comprise contacting said mixture With ureaand a urea solvent and separating from the resulting reaction mixture asolid, non-hydroscopic adduct of urea and said quaternary ammoniumcompound (I), substantially free from said quaternary ammonium compound(II).

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,346,632 Wolfert et al Apr. 11, 1944 2,518,677 Garner et alAug. 15, 1950 2,541,248 Hibbs Feb. 13, 1951 FOREIGN PATENTS NumberCountry Date 443,795 Great Britain Mar. 6, 1936 OTHER REFERENCESLawrence, Quaternary Ammonium Germicides (Academic Press, New York),1950, pp. 24-28. (Copy available in Pat. Off. Scientific Library.)

1. AN ADDUCT OF UREA AND A QUATERNARY DIMETHYLAMMONIUM COMPOUND HAVING AS SUBSTITUENTS ON THE NITROGEN ATOM THEREOF (1) AT LEAST ONE STRAIGHT-CHAIN ORGANIC RADICAL CONTAINING AT LEAST FIVE METHYLENE GROUPS AND (2) AN ALIPHATIC RADICAL CONTAINING NOT MORE THAN ONE CARBOCYCLIC-SUBSTITUENT, SAID CARBOCYCLIC SUBSTITUENT CONTAINING NOT MORE THAN SIX CARBON ATOMS IN THE RING, SAID QUATERNARY DIMETHYLAMMONIUM COMPOUND BEING OTHERWISE FREE FROM FUNCTIONAL GROUPS REACTIVE WITH UREA. 